DE20221830U1 - Solid-containing, water-absorbing, anionic polymers with sponge structure - Google Patents

Abstract

Particulate, earth-crumbly, water-absorbent and water-swellable solid, containing ground minerals and optionally further solid and / or liquid Additives, characterized in that the ground minerals, on Based on dry matter, at least 30 wt .-% and in a sponge-like, cross-linked polymer, the water and aqueous liquids under the formation of a hydrogel can absorb, are involved, and additionally water-soluble Alkali silicate is included.

Description

object the invention is a particulate, earth-crumbly, water-absorbent and water-swellable solid, containing ground minerals as plant nutrients, excipients and fiber, preferably and / or predominantly finely ground Igneous rocks as plant nutrients, and optionally in addition other solid and / or liquid Additives, characterized in that the mineral ingredients, based on dry matter, at least 30 wt .-% and in a sponge-like, cross-linked polymer, the water and aqueous liquids with the formation of a hydrogel are incorporated, and additionally water-soluble Alkali silicate is included. Furthermore, two simple procedures for the production of products of different degrees of neutralization presented and uses called.

By the type of preparation and the composition differ the products of the invention from the conventional ones Materials. externally the product particles have earthiness and are undried, Damp-moist condition directly comparable with humus. In the swelling process in aqueous liquids occurs due to the increase in the pore volume a suction effect, the one over the absorption capacity the polymer portion going liquid intake causes.

Hydrogel-forming polymers which take up water and aqueous liquids have already been frequently described. For the production, monoethylenically unsaturated, water-soluble carboxylic acids (eg acrylic acid) and their derivatives are used, usually after partial neutralization of the acid groups with alkali, together with one or more crosslinkers which have intramolecularly at least two ethylenically unsaturated groups. Either the polymerization is carried out in aqueous solution or by the processes of inverse suspension or emulsion polymerization, as in US 4,286,082 . DE-PS 27 06 135 . US 4,340,706 . DE-PS 28 40 010 have been described.

Further possibilities are offered by the preparation of graft polymers, for example using modified starch and cellulose ( DE-OS 26 12 846 ) or polyvinyl alcohol ( DE-PS 40 20 780 ) and the post-treatment of the polymer gels or of the pulverulent resins by post-crosslinking of the surfaces of the polymer particles, for example after DE-PS 40 20 780 C1 ,

When Comonomers are water-soluble, monoethylenic unsaturated Monomers such as acrylamide, methacrylamide, N-alkylated (meth) acrylamides, N-dialkylaminoalkylated (Meth) acrylamides, N-methylol (meth) acrylamide, N-vinylamides, N-vinylformamide, N-vinylacetamide and N-vinyl-N-methyl-acetamide, N-vinyl-N-methyl-formamide, vinylpyrrolidone, and the like Hydroxyalkyl (meth) acrylates such as hydroxyethyl acrylate and (meth) acrylic acid esters of polyethylene glycol monoallyl ether and allyl ether of polyethylene glycols used.

To EP 205 674 A1 An advantageous preparation is also described by subjecting a non-preaneutralized, aqueous monomer solution to the free-radical polymerization at temperatures in the range from 0 to 100 ° C., preferably 5 to 40 ° C., and only after thorough polymerization and comminution of the resulting hydrogel the desired degree of neutralization in Forced mixer is adjusted with alkali hydroxide solution.

All available in many different ways Polymers are also commonly used as superabsorbents called.

A preferred field of application for these suberabsorbers is the sanitary and sanitary sector. You can find them today among others in incontinence articles, baby diapers and tampons. It is obvious that skin neutrality and rapid as well as complete secretion absorption are required. The degrees of neutralization of the hydrogels are therefore between 50 and 80 mol%, based on the acid groups contained in the polymer. The spontaneity of the secretion absorption is achieved by a heat treatment of the previously dried and comminuted polymer particles in the presence of a postcrosslinking agent ( DE-PS 40 20 780 C1 ).

It it was obvious that for the hygiene sector obtained, hydrogel-forming polymers also to use as a water reservoir in the botanical sector. The transfer However, this area soon showed the diversity of Conditions.

In order to achieve good plant growth, the overall structure of the soil in combination with the superabsorbent also had to be considered. Terms such as soil climate and soil capillarity gained importance. Also, the mineral and nutrient supply necessary for the plants should be expediently taken into account and integrated. In addition, it turned out that the polymers were still very sensitive to alkaline earth and UV light. As in the German patent application with the file number 101 14 169 .6 reports, it was possible by the addition of alkali metal silicate to largely eliminate the last-mentioned property deficiencies of the polymers. The new task was to control the soil structure and the soil climate with the help of a polymer and solid material so that all the important conditions are met for growth.

By the product porosity becomes the soil capillarity improves and at the same time the soil quality through the presence of finely ground Minerals positively influenced.

It also puts the high mineral content a weighting of the superabsorbent so that a Flooding with high ground wetness omitted.

To achieve the desired product properties, the polymer-bound minerals in their nature and quantity can be varied within wide limits, but ground igneous rock is preferably present as a mineral plant nutrient and / or predominantly in the overall product. This rock is divided into two groups according to its calculated SiO ₂ content. The first group, here called A and basic, has an SiO ₂ content below 50 wt .-%, the second group, here B and acidic, an SiO ₂ content above 50 wt .-%. Since most of the product is to be neutral, basic group A igneous rocks are preferred. This is not least because it can be used to save alkali. Acidic Group B igneous rocks are desirable if the product of manufacture is to be used to treat ammoniacal and / or alkaline liquids or masses from the bacterial decomposition of organic substances (eg manure).

There the inorganic composition of the igneous rock, especially in terms of the trace elements, in conjunction with the particle size of the polymerization and thus affects the sponge structure of the manufactured product, it is necessary the influences to clarify the existing minerals on the basis of tests. There These minerals simultaneously the mineral nutrient source for the Plants, the degree of grinding should be chosen so that particle sizes below 200 mμ, preferably present under 100 mμ.

The subordinate to the igneous rock, additionally attached mineral Solids work during of the manufacturing process and when used in different ways Way, as can be seen from the following list. their However, use is not mandatory.

• a) säureempfindliche Hilfsstoffe als CO₂-Lieferant zur Inertisierung der Monomerenlösung: z. B. Kreide, Trass, Dolomit, Magnesit.
• b) Feststoffe als Verdickungsmittel, Schwammstabilisatoren, Kationenfänger, Polymerisationsverzögerer und Quellungsbeschleuniger: Wasserabsorbierende Tonminerale wie Bentonit.
• c) Ballast- und Füllstoffe: Mineralstoffe als natürliche Bestandteile der Erdkruste wie Feldspat, Quarzsand.

Additionally usable minerals, divided according to their functions, are:

• a) acid-sensitive excipients as CO ₂ supplier for the inertization of the monomer solution: z. Chalk, trass, dolomite, magnesite.
• b) Solids as thickeners, sponge stabilizers, cation scavengers, polymerization retarders and swelling accelerators: water-absorbing clay minerals such as bentonite.
• c) Ballast and fillers: minerals as natural components of the earth's crust, such as feldspar, quartz sand.

It is common, before the start of polymerization, the monomer solution of oxygen largely to free. Mostly this nitrogen is introduced for a long time. It turned out that carbonate-containing Minerals under the present conditions sufficient carbon dioxide can deliver, to carry out the polymerization and the desired sponge structure to create. If you refrain from these minerals, may alternatively Carbon dioxide introduced or carbonated water can be used.

minerals the group b) as bentonite possess the property, even small amounts of liquid (and thus monomer solution) to be able to record and cation binding ability to own. They therefore contribute to the strength and swelling behavior of the sponge. It must, however be aware that they polymerisationsverzögernd Act. Your particle size should be between 0.1 to 8 mm, preferably between 0.3 to 5 mm.

The Minerals of group c) are listed here, although they are used for the production of the product do not fulfill any special functions. However, since they belong to the solid mineral content of the product must be counted and may have a product-causing effect they are not missing here. For These fibers are no longer subject to special conditions, except that their Particle size of those the group b) adapted should be.

Of the Solid content of the product according to the invention is based on dry matter based, at least 30 wt .-%. The solids content includes the Group A and B igneous rocks as well as mineral solids the groups a) to c).

The for the Production of the total product necessary residual substances spread over the chemical components, neutralizing agents and Alkali silicate and optionally on K, N, P and Si-containing Fertilizer.

In carrying out the polymerization of a solids-containing, alkaline monomer solution was recognized that the previously homogeneously distributed solids can flocculate at the beginning of the polymerization, thereby significantly disturbing the sponge formation. For that reason, too sought a polymerization process that is as simple as possible in the implementation and in which flocculation and clumping of the solids no longer takes place. This problem was solved in various ways, which corresponded to the respective neutralization wish:
Method I: The minerals and non-polymerizing water-soluble components are presented as an aqueous, alkali carbonate and / or carbon dioxide-containing slurry which, in addition to avoid clumping, may contain an oxidizing catalyst, and the water-soluble ethylenically unsaturated acid group-containing monomers including the crosslinking agent and optionally the comonomers subsequently added, wherein carbon dioxide is released and foam is formed. After completion of the foaming the polymerization is carried out. Thereafter, the product is crushed.

A Further treatment is unnecessary if this product is for the absorption or treatment of ammoniacal and / or alkaline liquids is provided or over the amount of basic igneous rocks and solids used Group a) a plant tolerant pH range was reached. Otherwise, by treatment with alkaline earth metal and / or alkali hydroxide or mixing with lime or dolomite intercepted the excess acidity become.

As another method for producing neutral or alkaline pH products, which works with an optional amount of alkali and is similar in process to Method I, it is presented:
Process II: The minerals and the non-polymerizing components are dissolved as an aqueous slurry containing acid-neutralizing alkali substances such as alkali metal hydroxide, alkali metal carbonate and alkali metal silicate in such an amount that a maximum of 40 mol% of the ethylenically unsaturated acids are neutralized and optionally a further amount, which is contained in hydrophilic and / or porous solids, submitted. In order to prevent premature reaction of the optional amount with the acid groups of the monomer solution, this is additionally superficially z. B. encapsulated with wax. Thus, the neutralization before and during the polymerization can be delayed in time so that the formation of the sponge structure can take place undisturbed and still the amount of alkali necessary to achieve a degree of neutralization of 60 to 80 mol% contained in the product. The further procedure is as described under method I.

On This way will be acid to neutral or weak depending on your preference obtained alkaline products with stable sponge structure, the similar in pH neutral state like the superabsorbents big Absorb quantities of water. The water absorption is distributed on the pore space and the gel volume. When introduced into the ground comes it depending on the rainfall or water supply to a "breathing" of the soil, what in the presence of the mineral nutrient content of the product to an improved soil quality and a healthy soil climate leads.

To The countless ones offer the production and crushing of the product pore openings and bags the opportunity further solids of different particle sizes and Bulk weights, without Bearing and transport difficulties to be afraid to contribute. These can be igneous rocks and / or representatives of groups a) to c), but also organic Substances natural or of synthetic origin, designated as group N (non-mineral) to be named. Which includes in crushed form z. Algae, bast, lignite, hemp, wood, Castor, coal, straw, peat and water insoluble and water-swellable polymer products. By the possibility of the subsequent Introduction of different fillers There are also non-agricultural applications, which will be discussed later becomes. The opening and closing the bags can over the water content of the product are controlled.

As already mentioned above, the superabsorbents are water-absorbing polymers based on homo- and copolymers of monoethylenically unsaturated carboxylic acids. The latter can be supplemented by further ethylenically unsaturated monomers containing monomers. Specifically, to call:
Acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, sorbic acid, maleic acid, fumaric acid, itaconic acid, vinylsulfonic acid and acrylamido and Methacrylamidoalkylsulfonsäure such. For example, 2-acrylamido-2-methylpropanesulfonic acid, 2-methacryloyl-oxiethansulfonic acid, 4-vinylbenzenesulfonic acid, allylsulfonic acid, vinyltoluenesulfonic acid, vinylphosphonic acid and vinylbenzenephosphonic acid.

The abovementioned list of substances applies to the water-soluble, copolymerizable, ethylenically unsaturated monomers, so that they need not be repeated. The proportion of the comonomers can be up to 50 wt .-%, based on the polymerizable components of the monomer mixture. The monomer mixture may further contain water-soluble polymers up to 30 wt .-%, based on the polymerizable substance of the monomer mixture. Soluble polymers are: homopolymers and copolymers of the abovementioned monomers, partially saponified polyvinyl acetate, polyvinyl alcohol, starch, starch derivatives, Graft-polymerized starch, cellulose and cellulose derivatives such as carboxymethylcellulose, hydroxymethylcellulose and galactomannose and its oxalkylated derivatives.

The aqueous monomer solution contains at least a crosslinker in an amount of 0.01 to 5 wt .-%, preferably 0.1-2.0 Wt .-%, based on the totality of the polymerizable monomers. As a crosslinker, all substances can be used, at least two ethylenically unsaturated Groups or at least one ethylenically unsaturated group and at least contain another functional group that is resistant to acid groups is reactive. As representatives are called: Methylenbisacrylamid, Mono, di- and polyesters of acrylic acid, methacrylic acid, itaconic acid and Maleic acid of polyhydric alcohols such as butanediol, hexanediol, polyethylene glycol, Trimethylolpropane, pentaerythritol, glycerin and polyglycerol as well from the resulting oxyalkylated homologs as well as the Esters of these acids with allyl alcohol and its oxalkylated homologues. Continue to be listed: Diallylacrylamide, diallyl phthalate, triallyl citrate, trimonoallyl polyethylene glycol ether citrate and allyl ethers of di- and polyols and their ethoxylates. representative of the latter type are polyallyl ethers of glycerol, Trimethylolpropane, pentaerythritol and their Oxethylate as well as Tetraallyloxiethan and Polyglycidyl allyl ethers such as ethylene glycol diglycidyl ether and glycerol glycidyl ether. Finally, too also the amines and their salts with at least two ethylenically unsaturated Substituents listed These are di- and triallylamine and tetraallylammonium chloride.

to Initiation of the radical polymerization are redox systems used as common are to be classified, for. B. peroxo and azo compounds such as potassium peroxomonosulfate, Potassium peroxodisulfate, tert. Butyl hydroperoxide, 2,2'-azo-bis (2-methylenopropionamidine) dihydrochloride and hydrogen peroxide together with one or more reducing agents such as potassium sulfite, potassium formamidinesulfinate and ascorbic acid. in this connection the oxidizing agent is preferably initially introduced. At the operational Polymerization, the initiation preferably by photocatalysis and sensitizers.

There The products obtained after production in the form of blocks, is a crushing necessary before further use. The first step is usually a cutting, so that discs, mats or smaller blocks arise. If one remains with the mat form, can be further by Cutting or punching reach the most diverse forms. So can Square rods be prepared that the plant roots later the for the Growth necessary mineral and fertilizer needs deliver when they are placed in their food area. It can but also a shredder immediately be used, making the production of earthy crumbs directly possible is. These are particularly good in appearance and texture Humus adapted. In production fresh state is still a certain stickiness present, which can be exploited, the most diverse Shapes and structures by simply compressing the crumbs too produce.

The Products are for the growth, germination and cultivation of plants outstanding suitable and therefore also in the admixture in unfavorable soil and bad weather conditions good plant results. By the way, they also allow a limitation of irrigation intervals and are therefore beneficial, especially in low-rain crops. It is possible, the products of the invention also to be used alone for plant breeding. A special application is the use in plant containers, which are connected to a water reservoir by capillary rods and from which the product sponges Bring the water that is taken through the plant roots.

The Crumbs with their pores and pockets are a carrier for a wide variety of solids excellent. Of the many possible combinations should here the subsequent Mixture be called with castor meal. Castor bean drops Castor oil extraction and counts to solid fertilizers.

Is possible also a combination of a fertilizer-free Product with wood flour or wood shavings, which are then dried as "animal litter" for animal husbandry can be used.

Interesting would it be also, the crumbs later with fine grained, often dusty to equip synthetic polymer particles whose Use in pure form is usually problematic. By The adhesive effect of fresh crumbs can also be tissue or Equip non-corrosive floats and everywhere Use where water-absorbing products are bound and / or are asked fixed. Which includes Slope roofs, Side dishes for the Transport of goods and coffins.

Become these crumbly fabrics and fleeces additionally with buoyant natural and plastics these in wetlands for plant breeding such as rice cultivation and also to insect control with appropriate equipment be used.

It can be seen that the products of the invention due to their exceptional property and pocket structure are at the same time a synergy carrier and carrier material for a wide variety of solid and liquid products. So they are not just water storage and nutrient source.

The Invention is additional described by the facts stated in the claims.

EXAMPLES

• a) Eifellava: Eifelgold-Urgesteinsmehl, Fa. LAVA-UNION GmbH, 53489 Sinzig
• b) Trass: Fa. Märker-Zementwerk GmbH, 86665 Harburg
• c) Bentonit: Smektonit Agrarbentonit 0/8 der Fa. MARX Bergbau GmbH & Co., 5431 Ruppach-Goldhausen

The following solids were used:

• a) Eifellava: Eifelgold-Urgesteinsmehl, Fa. LAVA-UNION GmbH, 53489 Sinzig
• b) Trass: Messrs. Märker-Zementwerk GmbH, 86665 Harburg
• c) Bentonite: smectonite Agrarbentonite 0/8 of the company MARX Bergbau GmbH & Co., 5431 Ruppach-Goldhausen

The Chemicals were from the company Merck Eurolab GmbH, 44866 Bochum delivered.

Wako V-50 is available from Wako Chemicals GmbH, Neuss, Kaliwasserglas from Type 28-30 ° Bé at Fa. Baerle & Co., 76593 Gernsbach / Rhine.

Example 1:

40.0 g finely ground Eifellava, 15.0 g of finely ground trass and 15.0 g medium-ground bentonite are softened in 40.0 g, carbon dioxide-containing water stirred in homogeneously. Then, a monomer solution consisting from 15.0 g of acrylamide, 35.0 g of acrylic acid, 160 mg of 1,4-butanediol diacrylate and 30.0 g softened Water with stirring added in portions that the Foaming is dominated. When the foaming is complete, the polymerization will start by adding subsequent catalysts in the order given started: 1 ml of a 1.0 wt .-% solution of Wako V 50, 2 ml of a 1.0% by weight sodium peroxydisulfate solution, 1 ml of 0.2% by weight Ascorbic acid solution and 1 ml of a 1.25% by weight potassium bisulfite solution. The after the polymerization resulting polymer block takes after comminution only very limited Water up, as the acid groups of the polymer were not neutralized. Ammoniacal fluids however, are absorbed quickly and with good swellability. Become after chopping obtained crumbs in tap water of 20 ° dH, the 15.0 g of potassium hydroxide and Contains 3.0 g of potassium silicate, occurs over a period of 24 h an approximately 30-fold increase in weight.

Example 2:

40.0 g finely ground Eifellava, 15.0 g of finely ground trass and 15.0 g medium-ground bentonite are softened in 70.0 g, carbon dioxide-containing water stirred in homogeneously. Then 5 g of potassium water glass and a monomer solution, consisting of 50.0 g of acrylic acid and 160 mg of 1,4-butanediol diacrylate with stirring added in portions that the Foaming is dominated. After the fading of the foaming is initiated the polymerization analogously to Example 1. Will the after the chopping obtained crumbs placed in tap water of 20 ° dH, containing 21.5 g of potassium hydroxide results after 24 h almost a 40-fold increase in weight.

Example 3:

20.0 g of finely ground Eifellava and 5.0 g of medium-milled bentonite are softened in 70.0 g, carbon dioxide-containing water stirred in homogeneously. Then 5 g of potassium water glass and a monomer solution, consisting of 50.0 g of acrylic acid and 160 mg of 1,4-butanediol diacrylate are added in portions with stirring, that the Foaming is dominated. After the fading of the foaming is initiated the polymerization analogously to Example 1. Will the after the chopping obtained crumbs placed in tap water of 20 ° dH, containing 21.5 g of potassium hydroxide results after 24 h an approximately 60-fold increase in weight.

Example 4:

115 g finely ground Eifellava, 15.0 g of finely ground trass and 20.0 g medium-ground bentonite are softened into 64.0 g, carbonated water containing 12.0 g of potassium silicate, 14 g of potassium hydroxide (100%), 2.0 g of urea and 1.5 g of phosphoric acid (50%), homogeneous stirred. Subsequently 2 ml of a 1.0% by weight sodium peroxydisulfate solution are added. Then takes place under constant stir the registration of 50.0 g of acrylic acid, together with 0.2 g of 1,4-butanediol diacrylate. After the decay of the foaming the polymerization is started as in Example 1. After chopping, reach the crumbs after 24-hour storage in tap water of 20 ° dH 20 times your original one Weight.

Example 5:

100 g of finely ground Eifellava, 15.0 g of finely ground trass and 40.0 g of medium-milled bentonite / expanded clay mixture (1: 1), including 10.0 g of 50% by weight potassium hydroxide solution and 12.0 g of potassium silicate glass, and encapsulated with wax, are homogeneously stirred into 64.0 g of softened water containing 2.0 g of urea, 1.5 g of phosphoric acid (40%) and 14.0 g of potassium hydroxide (100%). Subsequently, 2 ml of a 1.0% strength by weight sodium peroxodisulfate solution are added. Then, with constant stirring, the entry of 50.0 g of acrylic acid, together with 0.2 g of butanediol diacrylate. After the foaming has subsided, the polymerization is started as in Example 1.

To the chopping reach the crumbs after 24 hours Storage in tap water of 20 ° dH 28 times its original Weight.

Example 6:

A Subset of 100.0 g from a batch analogous to Example 4 was chopped and the crumbs mixed with 15.0 g of calcium carbonate after preparation and partially dried. The mixed product was used as a plant substrate and revealed for Barley seeds excellent growing conditions.

Example 7:

A Subset of 100.0 g from a batch analogous to Example 4 was chopped and the crumbs mixed after production with 100.0 g of wood flour and partially dried. The mixed product gave animal litter.

Example 8:

A Subset of 100.0 g from a batch analogous to Example 4 was chopped and the crumbs mixed after production with 100.0 g of castor meal and partially dried. The product was used as a plant substrate in flower boxes.

Claims (17)

Particulate, earth-crumbly, water-absorbent and water-swellable solid, containing ground minerals and optionally further other solid and / or liquid additives, characterized in that the ground minerals, based on dry matter, at least 30 wt .-% and in a sponge-like, cross-linked polymer , which can absorb water and aqueous liquids to form a hydrogel, are involved, and in addition water-soluble alkali metal silicate is included. Solid according to claim 1, characterized in that that the minerals are selected are from plant nutrients, Excipients or fiber. A solid according to claim 1 or 2, characterized in that the minerals are selected from at least one of finely ground igneous rock; basic igneous rock with a calculated SiO ₂ content of less than 50% by weight; Acid igneous rock with a calculated SiO ₂ content above 50 wt .-%, chalk, dolomite, trass, magnesite and reaction products thereof with acid group-containing monomers with CO ₂ evolution; water-absorbing clay minerals such as bentonite; Feldspar or quartz sand. A solid according to claims 1 to 3, further comprising Thickeners, sponge stabilizers, cation scavengers, polymerization retarders and / or Quellungsbeschleuniger. A solid according to claims 1 to 4, further comprising additional solid ingredients selected from natural or synthetic organic products such as algae, bast, lignite, Hemp, wood, castor, coal, straw, peat and / or water insoluble and water-swellable polymer products. Solid according to Claims 1 to 5, characterized that the polymer contained therein was formed from a) From 55 to 99.9% by weight of at least one water-soluble, ethylenically unsaturated, acid groups containing monomers, b) 0 to 40 wt .-% of at least one water-soluble, ethylenically unsaturated, with the monomer of a) polymerizable comonomer, c) 0,01 to 5% by weight of at least one crosslinker and d) 0 to 30% by weight a water-soluble Polymer. Solid according to Claims 1 to 6, characterized that as water-soluble Alkali silicate potassium silicate is included as it is from the alkaline melt of quartz sand arises. Solid according to Claims 1 to 7, characterized that in addition at least one solid or liquid Representatives from the group of K-, N-, P-, Si-containing fertilizers is included. Solid according to claim 6, characterized that the water-soluble, ethylenically unsaturated acid groups containing monomers selected is from at least one of acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, sorbic acid, maleic acid, fumaric acid, itaconic acid, vinylsulfonic acid, and Acrylamido and methacrylamido-alkylsulfonic acids such as acrylamido-2-methylpropanesulfonic acid, 2-methacryloyl-oxyethansulfonic acid, 4-vinylbenzenesulfonic acid, allylsulfonic acid, vinyltoluenesulfonic acid, vinylphosphonic acid or Vinylbenzenephosphonic acid. Solid according to claim 9, characterized in that that the monomer is selected is made of acrylic acid, methacrylic acid and / or maleic acid. Solid according to Claims 1 to 10, characterized in that the water-soluble, ethylenically unsaturated comonomers is selected from at least one of acrylamide, methacrylamide, N-alkylated (meth) acrylamides, N dialkylamino-alkylated (meth) acrylamides, N-methylol (meth) acrylamide, N-vinylamides such as N-vinylformamide, N Vinylacetamide and N-vinyl-N-methyl-acetamide, N-vinyl-N-methylformamide and vinylpyrrolidone and hydroxyalkyl (meth) acrylates such as hydroxyethyl acrylate and (meth) acrylic acid esters of polyethylene glycol monoallyl ether and allyl ether of polyethylene glycols. Solid according to Claims 1 to 11, characterized in that the polymerisable, water-soluble, ethylenically unsaturated, acid groups containing monomers as potassium salts. Solid according to Claims 1 to 12, characterized that the minerals lava, tuff and / or diabase with a particle size below 200 micrograms, preferred below 100 μg are. A solid according to claims 1 to 13, obtainable by a method, characterized in that the medium to finely ground Minerals together with any non-polymerizing Components as aqueous, Alkaline earth carbonate, alkali carbonate and / or carbon dioxide-containing slurry submitted and at least one water-soluble, ethylenically unsaturated acid groups subsequently containing monomer and a crosslinking agent, with the slurry be reacted with liberation of carbon dioxide and subsequently, after completion of foaming, the polymerization is carried out, and finally the polymer block obtained was cut up and passed over a shredder or meat grinder so is crushed, that crumbs arise. Solid according to claim 14, characterized in that that in addition To prevent clumping an oxidizing catalyst added becomes. Solid according to claims 14 or 15, characterized that the monomer and the crosslinking agent optionally with the Comonomers are added together in the slurry. Solid according to Claims 14 to 16, characterized that the slurry is acid neutralizing Alkaline earth and alkali substances, preferably alkali metal hydroxide, alkali metal carbonate and alkali metal silicate, dissolved in such an amount that contains at most 40 mol% of the acid groups be neutralized.